EP0007931B2 - Mit Kautschuk modifizierte Terpolymere mit verbesserter Wärmeverformungsbeständigkeit - Google Patents

Mit Kautschuk modifizierte Terpolymere mit verbesserter Wärmeverformungsbeständigkeit Download PDF

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Publication number
EP0007931B2
EP0007931B2 EP78300909A EP78300909A EP0007931B2 EP 0007931 B2 EP0007931 B2 EP 0007931B2 EP 78300909 A EP78300909 A EP 78300909A EP 78300909 A EP78300909 A EP 78300909A EP 0007931 B2 EP0007931 B2 EP 0007931B2
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EP
European Patent Office
Prior art keywords
rubber
polymer
weight
percent
methacrylate
Prior art date
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Expired
Application number
EP78300909A
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English (en)
French (fr)
Other versions
EP0007931A1 (de
EP0007931B1 (de
Inventor
Yoon Chai Lee
Quirino Albert Trementozzi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Monsanto Co
Original Assignee
Monsanto Co
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Filing date
Publication date
Priority claimed from US05/927,429 external-priority patent/US4341695A/en
Application filed by Monsanto Co filed Critical Monsanto Co
Publication of EP0007931A1 publication Critical patent/EP0007931A1/de
Application granted granted Critical
Publication of EP0007931B1 publication Critical patent/EP0007931B1/de
Publication of EP0007931B2 publication Critical patent/EP0007931B2/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/02—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to elastomers

Definitions

  • This invention relates to terpolymers and specifically to styrene/maleic anhydride/methacrylate copolymers having a rubber modifier incorporated therein.
  • Rubber-modified styrenic polymers commonly referred to a HIPS are very tough and durable and have seen broad acceptance in a variety of uses such as appliance housings and the like.
  • HIPS begins to soften and lose its dimensional integrity under stress at temperatures below those at which it would be required to operate for a number of significant applications.
  • a rubber-modified styrenic terpolymer composition has now been discovered that produces a surprising improvement in the heat distortion temperature by comparison with HIPS making it suitable for a wide range of uses for which HIPS is disqualified.
  • the incorporation of the methacrylate termonomer has the effect of raising the tensile strength and the gloss of the rubber modified polymer in a most advantageous manner making the polymeric product most attractive for a broad spectrum of applications.
  • a polymeric composition comprising a rubber substrate polymer having a glass transition temperature below 0°C. grafted with a superstrate polymer and dispersed in a matrix polymer, the superstrate and matrix polymers each comprising a monoalkenyl aromatic monomer, an unsaturated dicarboxylic acid anhydride and a C, to C 3 alkyl methacrylate ester characterised in that there is present in the superstrate and matrix polymers from 45 to 83 percent by weight of the monoalkenyl aromatic monomer, from 15 to 35 percent by weight of the unsaturated dicarboxylic acid anhydride and from 2 to 20 percent by weight of the C, to C 3 alkyl methacrylate ester, that the amount of rubber in the composition, calculated as ungrafted substrate, is from 2 to 30 percent of the composition weight and that said rubber substrate is a polybutadiene comprising at least 90 percent of cis-1,4,-polybutadiene units.
  • a second advantage is that other physical properties such as multiaxial impact strength, tensile strength, elongation at fail and gloss of the polymer apparently increase with the amount of the methacrylate in the composition.
  • the preferred polymer compositions within this range will depend largely on the properties desired. Generally, however, the polymers containing from 4 to 10% by weight of the methacrylate comonomer are preparred. This is because the heat distortion temperature, as is explained later, initially increases rapidly with methacrylate content to a broad peak between about 7 and 1 5% content and thereafter begins a gradual decline. Thus, roughly the same improvement is generally obtained at 7% as at 15% methacrylate content. Additionally, it is preferred to retain the thermal stability as high as possible so as to permit more flexibility in the application of forming processes to the polymers.
  • the polymeric compositoin of the invention comprises a rubber substrate polymer having a glass transition temperature (Tg) below 0°C. grafted with a superstrate polymer and dispersed in a matrix polymer, the superstrate and the matrix polymers each comprising from 45 to 83% (preferably from 50 or 60 to 75%) by weight of a monoalkenyl aromatic monomer, from 15 to 35% (preferably 20-30%) by weight of an unsaturated dicarboxylic acid anhydride, and from 2 to 20% (preferably 4 to 10%) by weight of a C, to C 3 alkyl methacrylate ester, the amount of rubber in the composition, calculated as ungrafted substrate, being from 2 to 30% of the composition weight and the rubber substrate component ofthe polymeric composition being a polybutadiene which contains at least 90% by weight of cis 1,4-polybutadiene units.
  • Tg glass transition temperature
  • the monoalkenyl aromatic monomer is preferably styrene but styrene derivatives such as alphamethylstyrene, chlorostyrene, 2,4-dichlorostyrene and 2-chloro-4-methylstyrene may be substituted for styrene in whole or in part if desired.
  • the unsaturated dicarboxylic acid anhydride is most preferably maleic anhydride though any of the homologues of mallic anhydride such as itaconic, citraconic and aconitic anhydrides can also be used.
  • the polymeric composition further comprises a C, to C 3 alkyl ester of methacrylic acid.
  • the methacrylic ester can be methyl methacrylate, ethyl methacrylate or propyl methacrylate.
  • the preferred copolymerizable monomer is methyl methacrylate.
  • the polymeric composition is conveniently prepared by dissolving the rubber in a solution of the monoalkenyl aromatic component and the methacrylate ester in a suitable solvent, and then polymerizing the solution with the anhydride component in the manner described in, for example, U.S.P. 2,971,939, U.S.P. 3,336,267 and U.S.P. 3,919,354.
  • a suitable polymerization schedule can be devised on the basis of the relative reactivities of the monomers. Typical schedules involve preparing an initial reaction mixture comprising a solvent, the bulk of the alkenyl aromatic monomers, a very small amount (or none) of the anhydride monomer and the major portion of the methacrylate termonomer. The rubber is dissolved in this mixture and the balance of the monomers is added slowly during the polymerization.
  • the amount of rubber substrate (ungrafted basis) in the polymeric composition, which includes the grafted superstrate and any matrix polymer present, is in the range from 2 to 30% by weight based on the weight of the polymeric composition. Preferably, however, the rubber substrate represents from 5 to 25% of the weight of the polymeric composition.
  • antioxidant stabilizers for styrenic polymers is available but particularly satisfactory results can be obtained using 1,3,5-trimethyl-2,4,6-tris[3,5-di-tert-butyl-4-hydroxybenzyl]benzene and 2,2'-methyiene-bis-(4-methyi-6-tert-butyi phenol)terephthalate.
  • the rubber component usually requires a different stabilizer such as a tris(alkylphenyl)phosphite though the prior art can supply others that would be effective. '
  • the total amount of stabilizer that may be used is not critical but up to 5% by weight based on the total composition is usually found to be adequate. In general 0.1 to 2% is the range chosen for practical advantage.
  • the polymeric composition can contain other additives such as for example, additional ungrafted rubber components such as the so-called block rubbers and radial block rubbers, flame retardants, smoke suppressants, U.V. stabilizers, lubricants, antistatic additives, colorants and fillers.
  • additional ungrafted rubber components such as the so-called block rubbers and radial block rubbers, flame retardants, smoke suppressants, U.V. stabilizers, lubricants, antistatic additives, colorants and fillers.
  • the polymer compositions are described on the basis of a combination of elemental analysis and titrimetric analysis techniques.
  • the rubber concentration is determined on the basis of material balances in the polymer composition. Unless otherwise stated the rubber used was a medium-cis polybutadiene rubber available from Firestone Corp. under the trade name "Diene 55".
  • the Examples illustrate the results of varying the amount of the methacrylate ester in the composition and the surprising advantages obtained by maintaining the level in the range of 2 to 20% by weight.
  • the multiaxial impact strength is shown. This is commonly called the F.D.I. and is measured according to ASTM D-1709 on a sample 2.9 mm in thickness.
  • the Izod impact strengths were measured using 3.2 x 12.7 x 63.5 mm unannealed compression molded samples, notched 2.54 mm.
  • the DTUL values given are for 3.2 x 12.7 x 127 mm unannealed compression molded samples tested under a 18.6 kg/sq.cm. stress.
  • Unannealed compression molded samples were chosen in preference to injection molded samples so as to eliminate the variations that occur in the preparation of injection molded samples which become partially oriented during the forming process.
  • the choice of unannealed compression molded samples which are not oriented during formation eliminates, one result-affecting variable and makes the comparison more significant.
  • Example 1 The polymer used in Example 1 was prepared as follows: An agitated resin kettle was charged with 323 g. of styrene, 15 g. of methyl methacrylate, 0.1 g. of trisnonylphenyl phosphite (a stabilizer for the rubber) and a solvent mixture consisting of 50 g. of methyl ethyl ketone (MEK) and 75 g. of toluene. In this mixture were dissolved 54 g. of a high cis polybutadiene rubber. After the rubber was completely dissolved, a solution of 4 g. of maleic anhydride in 25 g. of MEK was added. The reaction mixture was raised to 85°C. and maintained at that level for the entire reaction period.
  • MEK methyl ethyl ketone
  • the polymer was then separated from the solvent and the residual monomer removed by a conventional method.
  • the isolated polymer was blended with any desired additives, such as stabilizers, and compression molded into samples for evaluation.
  • compositions contained 0.3% by weight of 1,3,5-trimethyl-2,4,6-tris[3,5-di-tert-butyl-4-hydroxybenzyl]benzene as an antioxidant stabilizer.
  • Examples 1-3 and 6 used high-cis rubber while Examples 4 and 5 (Comparative) used the medium-cis rubber described above.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Claims (3)

1. Polymer-Zusammensetzung, enthaltend ein Kautschuk-Substratpolymer mit einer Glasübergangstemperatur untehralb von 0°C, welches mit einem Superstrate-Polymer gepfropft ist und in einem Matrixpolymer dispergiert ist, wobei das Superstrate-Polymer und das Matrixpolymer jeweils ein Monoalkenyl-Aromaten-Monomer, ein ungesättigtes Dicarbonsäureanhydrid und einen C,C3-Alkylmethacrylatester enthalten, dadurch gekennzeichnet, daß in dem Superstrate-und in dem Matrixpolymer 45 bis 83 Gew.-% des Monoalkenyl-Aromaten-Monomers, 15 bis 35 Gew.-% des ungesättigten Dicarbonsäureanhydrids und 2 bis 20 Gew.-% des C1―G3-Alkylmethacrylatesters vorhanden sind, daß die Menge des Kautschuks in der Zusammensetzung, berechnet als nicht gepfropftes Substrat, 2 bis 30% des Gewichtes der Zusammensetzung beträgt, und das Kautschuksubstrat ein Polybutadien ist, welches mindestens 90% cis-1,4-Polybutadieneinheiten enthält.
2. Polymer-Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das C1―C3-Alkylmethacrylat Methylmethacrylat ist.
3. Polymer-Zusammensetzung nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß in dem Superstrate- und in dem Matrixpolymer 4 bis 10 Gew.-% des C1―C3-Alkylmethacrylatesters vorhanden sind.
EP78300909A 1978-07-24 1978-12-27 Mit Kautschuk modifizierte Terpolymere mit verbesserter Wärmeverformungsbeständigkeit Expired EP0007931B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US927429 1978-07-24
US05/927,429 US4341695A (en) 1977-12-27 1978-07-24 Rubber modified terpolymers with improved heat distortion resistance

Publications (3)

Publication Number Publication Date
EP0007931A1 EP0007931A1 (de) 1980-02-20
EP0007931B1 EP0007931B1 (de) 1982-05-12
EP0007931B2 true EP0007931B2 (de) 1984-11-28

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP78300909A Expired EP0007931B2 (de) 1978-07-24 1978-12-27 Mit Kautschuk modifizierte Terpolymere mit verbesserter Wärmeverformungsbeständigkeit

Country Status (8)

Country Link
EP (1) EP0007931B2 (de)
JP (1) JPS5518479A (de)
AU (1) AU520708B2 (de)
BR (1) BR7808510A (de)
CA (1) CA1121084A (de)
DE (1) DE2861838D1 (de)
IT (1) IT1102788B (de)
MX (1) MX150448A (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS582313A (ja) * 1981-06-30 1983-01-07 Daicel Chem Ind Ltd 耐熱・耐衝撃性樹脂の製造方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2858281A (en) * 1954-01-22 1958-10-28 Goodrich Co B F Insoluble, acid and alkali-resistant carboxylic polymers
US3676526A (en) * 1967-06-02 1972-07-11 Eugene G Sommerfeld Polymeric dispersion of a diene-acrylonitrite graft copolymer with a different graft copolymer
CA882187A (en) * 1968-03-13 1971-09-28 Farbenfabriken Bayer Aktiengesellschaft Thermoplastic-elastic moulding compounds
US3919354A (en) * 1972-09-08 1975-11-11 Dow Chemical Co Impact resistant polymers of a resinous copolymer of an alkenyl aromatic monomer and unsaturated dicarboxylic anhydride
US3832274A (en) * 1973-06-06 1974-08-27 Lord Corp Fast curing adhesives
DE2329585C2 (de) * 1973-06-09 1984-01-05 Bayer Ag, 5090 Leverkusen Polycarbonat-Formmassen
US3900528A (en) * 1973-10-09 1975-08-19 Monsanto Co Process for impact modification of high nitrile polymers
US3900529A (en) * 1973-10-09 1975-08-19 Monsanto Co Rubber modified high nitrile polymers and polymer blends produced thereby
IT1043117B (it) * 1975-10-03 1980-02-20 Snam Progetti Resine antiurto e metodo per la loro areparazione
JPS52112692A (en) * 1976-03-19 1977-09-21 Toyo Soda Mfg Co Ltd Method for carboxylation of ethylene-vinyl acetate copolymers
US4097551A (en) * 1976-12-20 1978-06-27 Arco Polymers, Inc. Rubber modified dicarboxylic acid copolymer blends

Also Published As

Publication number Publication date
JPS6219446B2 (de) 1987-04-28
IT1102788B (it) 1985-10-07
DE2861838D1 (en) 1982-07-01
CA1121084A (en) 1982-03-30
BR7808510A (pt) 1980-05-20
AU520708B2 (en) 1982-02-25
MX150448A (es) 1984-05-09
JPS5518479A (en) 1980-02-08
EP0007931A1 (de) 1980-02-20
AU4292178A (en) 1980-01-31
IT7831344A0 (it) 1978-12-27
EP0007931B1 (de) 1982-05-12

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